KR19990066740A - Water pollution inhibitor and antifouling paint containing this water pollution inhibitor - Google Patents

Abstract

The water pollution inhibitor includes an hexacyano compound, preferably hexacyano ferrate, as an active ingredient. Antifouling agents are useful for the preparation of antifouling paints.

Description

Water pollution inhibitor and antifouling paint containing this water pollution inhibitor

The present invention relates to an antifouling agent effective in preventing aquatic organisms such as algae, oysters, mussels, etc. from adhering to seawater such as ships, marine structures, fishing nets, and the like, and an antifouling paint using the same.

In general, ship bottoms, marine structures, fishing nets, fish tanks, etc., have been in contact with sea water for a long time. In the meantime, since sea creatures such as seaweed, oysters, and mussels adhere to the seawater contact surface of such an object, in ships, the increase in weight, the decrease in the operating speed due to the increase of the water flow resistance, and the fishing nets and marine structures And the number of years of service has declined significantly. Therefore, the method of preventing adhesion of these marine organisms is conventionally performed. For example, chemical or biochemical methods are known by the use of materials that are difficult to attach to marine organisms such as copper plates, silicone resin coatings, and fluorine-based coatings, repellents of marine organisms, and antifouling agents. Even in such a pollution prevention means, the application area is wide, a high effect can be obtained, and the process is easy, and the method of apply | coating the antifouling paint containing an antifouling agent etc. to a ship is generally performed. Background Art [0002] Conventionally, antifouling paints in which organic tin compounds, organic tin polymers, and copper oxides are mixed with a binder component composed of polymers such as insoluble acrylic resins, alkyd resins, rubber chlorides, and rosin in seawater have been provided.

Paints containing organic tin compounds or organic tin polymers gradually elute the organic tin compounds or organic tin polymers in the paint, or the paint containing them gradually flakes and spreads into the water, and new paint surfaces are always exposed. Since the organic tin compound and the organic tin polymer are eluted in water, there is a problem of safety hygiene and environmental preservation.

The present invention eliminates the above-mentioned defects and prevents the accumulation of various marine organisms such as oysters and mussels on the surface of the seawater contact portion, marine structure, fishing net, etc. of the ship for a long time, An object of the present invention is to provide an excellent antifouling agent for environmental preservation and an antifouling paint containing the antifouling agent.

That is, the present invention provides, on the one hand, a water pollution inhibitor comprising an hexacyano compound, or a hexacyano compound and copper nitrite as an active ingredient, and on the other hand, a contamination comprising a paint component and the water pollution inhibitor. Provide prevention paint.

In the present invention, it is preferable that the hexacyano compound is hexacyano ferrate in view of bioadhesion resistance, elution resistance, and the like.

The anti-fouling agent according to the present invention provides a paint having excellent storage stability without promoting gelation in the paint composition. Moreover, the antifouling paint effective from the water pollution inhibitor of the present invention shows excellent antifouling property over a long period of time. Due to the use of hexacyano compounds that are stable in water, aquatic antifouling agents can maintain a prophylactic effect on the attachment of plants and animals to live in seawater without substantial problems of safety and hygiene over the long term.

EMBODIMENT OF THE INVENTION The present invention will be described in more detail with reference to preferred embodiments below.

Although the water pollution inhibitor of this invention may be used directly as it is, generally, it is used disperse | distributing in coating film forming resins, such as an acrylic resin, a rubber chloride, and a vinyl resin.

In particular, the water pollution prevention agent of the present invention is useful when blended into a suitable paint composition and used as an antifouling paint for large vessels or marine structures such as used by being immersed in water. In other words, the hexacyano compound may be dissolved or dispersed in a coating film forming component to form a paint to be used as a bottom paint and a pollution prevention paint for fishing facilities.

Examples of the hexacyano compound used in the present invention include potassium hexacyanochromate (III), potassium hexacyanocobalt (III), ammonium hexacyano iron (II), and hexacyano iron (III). Ammonium acid, potassium hexacyano iron (II), potassium hexacyano iron (III), sodium hexacyano iron (II), sodium hexacyano iron (III), hexacyano iron (II) Sodium potassium oxide, iron hexacyano iron (II), copper hexacyano iron (II), iron hexacyano iron (III), sodium hexacyanomanganate (II), etc. may be used. And environmental conservation, in particular iron hexacyano iron (II), iron hexacyano iron (III), iron Ⅱ, hexacyano iron (II), iron (III) and hexacyano iron (III) At least one hexacyano iron salt selected from the sodium salt, potassium salt, ammonium salt of (III) or these complex salts is preferable.

The antifouling agent of the present invention may be a single hexacyano compound alone or a mixture of two or more thereof, but a combination of one or more of these hexacyano compounds and copper nitrate can be efficiently used thereon. Used. The cuprous oxide used in the present invention is a red powder, also called cuprous oxide, which is generally used for preventing contamination of boat bottom paints and fishing nets. The amount of cuprous oxide used in combination with the hexacyano compound is preferably 1 to 10,000 parts by weight based on 100 parts by weight of the hexacyano compound.

Examples of the coating film forming resin used in the antifouling paint of the present invention include acrylic resins, epoxy resins, polyester resins, epoxy resins, butyral resins, vinyl resins, polyurethane resins, urea resins, and the like. Ethylene-vinyl acetate type resin etc. are mentioned.

Regarding the amount of the hexacyano compound used or the total amount of the hexacyano compound and the cuprous oxide used in the antifouling paint of the present invention, 2 to 80% by weight relative to the solid content of the coating film-forming resin in the antifouling paint. Preferably it is mix | blended in the ratio of 5 to 60 weight%. If it is less than 2% by weight, the effect of preventing bioadhesion can not be sufficiently obtained, and if it is more than 80% by weight, the physical properties of the coating film are lowered, which is not preferable.

In order to prepare the antifouling paint of the present invention, the coating film forming resin is dissolved in water, methanol, ethanol, propanol, isopropanol, butanol, ethyl acetate, butyl acetate, methyl ethyl ketone, acetone, xylene, toluene, ethyl cellosolve, and the like. Or it disperse | distributes, it mix | blends a hexacyano compound, and adds a dispersing agent, a hardening | curing agent, a hardening accelerator, etc. on it as needed, and is prepared.

EXAMPLE

Next, the present invention will be described in detail with reference to experimental examples, examples and comparative examples.

Experimental Example

Preparation of water pollution inhibitor (hexacyano compound)

Experimental Example 1

To a 3000 m1 beaker equipped with a stirrer and a thermometer, 500 m1 of water, 60 g of sulfuric acid, 44 g of ammonium sulfate and 100 g of ferrous sulfate were dissolved to dissolve the contents, and water was added thereto to prepare a liquid amount of 1200 m1. Then, the temperature is raised to make the liquid temperature 90 ° C. On the other hand, 600 ml of water is put into a 1000 m1 beaker prepared separately, and 160 g of sodium ferrocyanide dehydrates are dissolved, and the liquid temperature is heated to 80 ° C.

Subsequently, while stirring the ferrous sulfate solution, the sodium ferrocyanide solution is poured for 10 minutes. After pouring, set the liquid temperature to 95-98 ° C and keep it for 1 hour. Next, the solution which melt | dissolved 6.4 g of sodium chlorate in 50 m1 of water is added to this liquid mixture, and stirring is continued for 1 hour. Furthermore, 400m1 of cold water was added to this reaction liquid, and it filtered. The filter cake obtained is further washed three times with 2000 m1 of water. After drying this filter cake at 60 degreeC for 16 hours, it was grind | pulverized and the water pollution inhibitor A was obtained.

Experimental Example 2

To a 3000 m1 beaker equipped with a breeder and a thermometer, 500 m1 of water, 60 g of sulfuric acid, and 100 g of ferrous sulfate heptahydrate are added to dissolve the contents, and water is added thereto to prepare a liquid amount of l200 m1. Then, the temperature is raised to make the liquid temperature 90 ° C. On the other hand, 600 ml of water is put into a 1000 m1 beaker prepared separately, 115 g of potassium ferrocyanide trihydrate is melt | dissolved, and liquid temperature is heated to 80 degreeC.

Subsequently, while stirring the ferrous sulfate solution, the potassium ferrocyanide solution is poured into it for 10 minutes. After pouring, set the liquid temperature to 95-98 ° C and keep it for 1 hour. Next, the solution which melt | dissolved 6.4 g of sodium chlorate in 50 ml of water is added to this liquid mixture, and stirring is continued for 1 hour. Furthermore, 400m1 of cold water was added to this reaction liquid, and it filtered. The filter cake obtained is further washed three times with 2000 m1 of water. After drying this filter cake at 60 degreeC for 16 hours, it was grind | pulverized and the water pollution inhibitor B was obtained.

Experimental Example 3

500m1 of water, 60g of sulfuric acid, 44g of ammonium sulfate, and 58g of copper sulfate were added to a 3000m1 beaker equipped with a stirrer and a thermometer to dissolve the contents, and water was added thereto to prepare a liquid amount of 1200 ml. Then, the temperature is raised to make the liquid temperature 90 ° C. On the other hand, 600 ml of water are put into a separately prepared l000 ml beaker, and 160 g of sodium ferrocyanide pentahydrate is dissolved, and the liquid temperature is raised to 80 ° C.

Subsequently, while stirring the ferrous sulfate solution, the sodium ferrocyanide solution is poured for 10 minutes. After pouring, set the liquid temperature to 95-98 ° C and keep it for 1 hour. Furthermore, 400 ml of cold water was added to this reaction liquid, and it filtered. The filter cake thus obtained was further washed three times with 2000 m1 of water. After drying this filter cake at 60 degreeC for 16 hours, it was grind | pulverized and the water pollution inhibitor C was obtained.

Experimental Example 4

To a 3000 m1 beaker equipped with a stirrer and a thermometer, 500 m1 of water, 60 g of sulfuric acid, 44 g of ammonium sulfate and 100 g of ferrous sulfate were dissolved to dissolve the contents, and water was added thereto to prepare a liquid amount of 1200 ml. Then, the temperature is raised to make the liquid temperature 90 ° C. On the other hand, 600 m1 of water is put into a 1000 ml beaker prepared separately, 160 g of sodium ferrocyanide dehydrates are melt | dissolved, and liquid temperature is heated to 80 degreeC.

Subsequently, while stirring the ferrous sulfate solution, the sodium ferrocyanide solution is poured for 10 minutes. After pouring, set the liquid temperature to 95-98 ° C and keep it for 1 hour. Furthermore, 400 ml of cold water was added to this reaction liquid, and it filtered. The filter cake thus obtained was further washed three times with 2000 m1 of water. The filter cake was dried at 60 ° C. for 16 hours, and then ground to obtain an antifouling agent D in water.

Experimental Example 5

To a 3000 ml beaker equipped with a stirrer and a thermometer, 500 ml of water, 60 g of sulfuric acid, 44 g of ammonium sulfate and l00 g of ferrous sulfate were dissolved to dissolve the contents, and water was added thereto to prepare a liquid amount of 1200 m1. Then, the temperature is raised to make the liquid temperature 90 ° C. On the other hand, 600 m1 of water is put into a 1000 ml beaker prepared separately, 160 g of sodium ferrocyanide pentahydrates are melt | dissolved, and liquid temperature is heated to 80 degreeC.

Subsequently, while stirring the ferrous sulfate solution, the sodium ferrocyanide solution is poured for 10 minutes. After pouring, set the liquid temperature to 95-98 ° C and keep it for 1 hour. Next, the solution which melt | dissolved 6.4 g of sodium chlorate in 50 m1 of water is added to this liquid mixture, and stirring is continued for 1 hour. Furthermore, 400m1 of cold water was added to this reaction liquid, and it filtered. The filter cake thus obtained was further washed three times with 2000 m1 of water. 6 g of triethylenetetramine was added to the filter cake, mixed with 50 ml of water for 10 minutes with a mixer (juicer), dried at 60 ° C. for 16 hours, and then ground to obtain an antifouling agent E in water.

Experimental Example 6

To a 3000 m1 beaker equipped with a stirrer and a thermometer, 500 m1 of water, 60 g of sulfuric acid, 44 g of ammonium sulfate and l00 g of ferrous sulfate were dissolved to dissolve the contents, and water was added thereto to prepare a liquid amount of 1200 m1. Then, the temperature is raised to make the liquid temperature 90 ° C. On the other hand, 600m1 of water is put into the separately prepared l000m1 beaker, 160g of sodium ferrocyanide pentahydrates are dissolved, and the liquid temperature is heated to 80 degreeC.

Subsequently, while stirring the ferrous sulfate solution, the sodium ferrocyanide solution is poured for 10 minutes. After pouring, set the liquid temperature to 95-98 ° C and keep it for 1 hour. Furthermore, 400m1 of cold water was added to this reaction liquid, and it filtered. The filter cake obtained is further washed three times with 2000 ml of water. 6 g of triethylenetetramine was added to the filter cake, mixed with 50 ml of water for 10 minutes with a mixer (juicer), dried at 60 ° C. for 16 hours, and then ground to obtain an antifouling agent F in water.

Experimental Example 7

100 g of copper nitrite was blended with 100 g of the water pollution inhibitor (C) obtained in Experimental Example 3 to obtain an underwater pollution inhibitor G.

Bioaccumulation Prevention Evaluation Test

Examples 1-7

In each Example, Experimental example 1-experiment example were carried out to the mixture of phthalic-acid resin varnish (brand name: J-557 Varnish Nippon Chemical Co., Ltd.) 9.0g, mineral terpene 4.5g, and glass bead (3mm diameter) 52.5g. 3.0 g of 1 type of water pollution inhibitors A-G obtained by the experiment example of a corresponding number in 7 is mix | blended, and it puts into a 100 ml1 sample bottle made from polyethylene with a sealing stopper, and stirred for 60 minutes with a paint shaker. Subsequently, 51.0 g of the above-mentioned phthalic acid resin varnish is added, followed by stirring for 5 minutes with a paint shaker.

0.42 g of a drying agent (composed of 50 parts by weight of cobalt naphthenate, 27 parts by weight of lead naphthenate and 23 parts by weight of xylene) was added and mixed to the obtained coating liquid. Each coating liquid thus obtained is brushed onto a 300 mm × 200 mm × 3.2 mm iron plate subjected to sand blast treatment.

After the iron plate is dried at room temperature overnight, the coating film is brushed again on the coating film and dried at room temperature overnight to prepare a test piece.

Comparative Example 1

A test piece was prepared in the same manner as in Example, except that the coating liquid used without the water pollution inhibitor used in Examples 1 to 7 was used.

Comparative Example 2

A test piece was prepared in the same manner as in Example except that 3.0 g of copper nitrous oxide was used alone instead of the water pollution inhibitor used in Examples 1 to 7.

"evaluation"

Four pieces of test pieces obtained in Examples and Comparative Examples were set on a 600 mm × 1100 mm edge made of 3/4 B stainless steel pipe, and these were immersed in seawater at a water temperature of about 10 to 20 ° C. for 1 month, 3 months, and 6 months. After the elapsed time, the adherence state of oyster lamp, slime and seaweed was observed. The results are shown in Table 1.

Table 1

Water pollution inhibitor 1 month later 3 months later 6 months later Example 1 A Nothing attached Slime slightly attached Some algae, oysters stick Example 2 B Nothing attached Slime slightly attached Some algae, oysters stick Example 3 C Nothing attached Slime slightly attached Some algae, oysters stick Example 4 D Nothing attached Nothing attached Algae attached Example 5 E Nothing attached Nothing attached Algae attached Example 6 F Nothing attached Nothing attached Algae attached Example 7 G Nothing attached Nothing attached Algae attached Comparative Example 1 none Algae, oysters stick High density of oysters, seaweed Oysters stick remarkably Comparative Example 2 Cuprous oxide alone Slime slightly attached Slime attaches thickly Algae, oysters attach

Example 8

To 100 g of a solution of 65 parts by weight of rosin, 25 parts by weight of linseed oil and 10 parts by weight of linseed oil fatty acid with 100 parts by weight of mineral spirits, 30 g of water pollution inhibitor E, 25 g of iron group, 2 g of manganese naphthenate, and 2 g of lead naphthenate Was mixed and dispersed for 20 minutes using a batch attritor to prepare the bottom paint 2. The above-mentioned bottom blast paint No. 2 was brushed on the sandblasted iron plate which previously applied the bottom rust-proof paint for commercial bottoms, and it dried at room temperature for 5 days, and created the test piece.

Example 9

A test piece was prepared in the same manner as in Example 8 except that the water pollution inhibitor F was used in place of the water pollution inhibitor E used in Example 8.

Comparative Example 3

A test piece was produced in the same manner as in Example 8 except that 30 g of copper nitrous oxide was used in place of the water pollution inhibitor E used in Example 8.

Example 10

12 parts by weight of linseed oil, 12 parts by weight of kerosene, 32 parts by weight of ester gum, 40 parts by weight of iron, 20 parts by weight of creosote oil, 40 parts by weight of water pollution inhibitor F, 42 parts by weight of mineral spirit and those used in Examples 1 to 7 As described above, 2 parts by weight of the desiccant was mixed and dispersed for 20 minutes using a batch arbiter to prepare a neckline bottom paint.

Grind the entire surface of the wood piece (200mm × 200mm × 10mm) of sufficiently dried pine tree prepared separately, brush it on the bottom of the wooden boat, dry it for 24 hours, and then brush it twice on it for 7 days. The test piece was made by drying at room temperature.

Example 11

A test piece was produced in the same manner as in Example 10 except that the water pollution inhibitor G was used in place of the water pollution inhibitor F used in Example 100.

Comparative Example 4

A test piece was produced in the same manner as in Example 10 except that the water pollution inhibitor F used in Example 10 was removed from the formulation.

"evaluation"

The test pieces obtained in Example 8, Example 9 and Comparative Example 3, Example 10, Example 11 and Comparative Example 4 were fixed to a mount and immersed in seawater at a water temperature of about 20 to 25 ° C. for 30 days and 90 days. And adherence state of oyster lamp, slime and seaweed on the surface of test piece after 180 days. The results are shown in Table 2.

TABLE 2

Water pollution inhibitor 1 month later 3 months later 6 months later Example 8 E Nothing attached Slime slightly attached Some algae, oysters Example 9 F Nothing attached Nothing attached Some algae, oysters Comparative Example 3 Cuprous oxide Nothing attached Slime Attached Algae, oysters, etc. attach a lot Example 10 F Nothing attached Slime slightly attached Some algae, oysters Example 11 G Nothing attached Nothing attached Algae slightly attached Comparative Example 4 none Some algae, oysters stick Algae, oysters attach Algae, oysters are attached in large quantities

The anti-fouling agent according to the present invention provides a paint having excellent storage stability without promoting gelation in the paint composition. Moreover, the antifouling paint effective from the water pollution inhibitor of the present invention shows excellent antifouling property over a long period of time. Due to the use of hexacyano compounds that are stable in water, aquatic antifouling agents can maintain a prophylactic effect on the attachment of plants and animals to live in seawater without substantial problems of safety and hygiene over the long term.

Claims (8)

A water pollution preventing agent comprising a hexacyano compound as an active ingredient. The water pollution preventing agent according to claim 1, wherein the hexacyano compound is hexacyano ferrate. 3. The hexacyano ferrate salt according to claim 2, wherein the hexacyano ferrate salt is iron (II) hexacyano iron (II), iron hexacyano iron (III) acid (II), iron hexacyano iron (II) iron (III) or An anti-fouling agent comprising at least one hexacyano ferrate selected from the group consisting of sodium salts, potassium salts, ammonium salts, or a complex salt of iron hexacyano iron (III). The anti-fouling agent according to any one of claims 1 to 3, further comprising copper nitrate as another active ingredient. An antifouling paint comprising the water pollution inhibitor according to any one of claims 1 to 4 and a coating component. 6. The paint component according to claim 5, wherein the paint component is an acrylic resin, a vinyl chloride-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, an epoxy resin, a vinyl chloride resin, a polyurethane resin, a silicone resin, a styrene resin, Anti-fouling paint, characterized in that comprising at least one resin selected from the group consisting of polyester resins. Use of the anti-fouling agent according to any one of claims 1 to 4 for preventing aquatic organisms from adhering to a part in contact with water. Use of the antifouling paint according to claim 5 or 6 for preventing aquatic organisms from adhering to water-contacting parts.